KR100325124B1 - Fungicide composition and sterilization method using the same - Google Patents

Abstract

The present invention provides a biocide composition consisting of 3-isothiazolone of General Formula (1) and polyhexamethyleneguanidine phosphate of General Formula (2) in order to provide a biocide composition which not only does not corrode metal, but also has a high instant sterilizing capability, a wide antibiotic spectrum, and superior antiseptic effects: where R is hydrogen or chlorine in General Formula (1), and m is an integer from 4 to 7 and n is an integer from 1 to 14 in General Formula (2).

Description

Fungicide composition and sterilization method using the same

The present invention relates to a disinfectant composition, and more particularly to a synergistic disinfectant composition comprising 3-isothiazolone and polyhexamethyleneguanidine phosphate and a method for sterilizing microorganisms, fungi and the like using the same.

Industrial water, such as cooling water, wastewater, and emulsions used in the textile industry, grows microorganisms, bacteria, molds, algae, and the like, which hinders efficient operation of industrial processes. Among them, microorganisms multiply by using organic substances contained in industrial water as nutrients, secrete polysaccharides, and various organic and inorganic substances are combined with these secreted polysaccharides to form viscous mass called slime. In particular, in the papermaking process, cellulose, hemicellulose and organic matter present in white water become rich nutrients for microorganisms, so slimes are formed in the part where the flow of fluid is weakened. This can lead to direct and indirect losses such as loss of equipment and efficiency of the device. In addition, in the case of an industrial cooling tower, as a large amount of water gathers like a cooling water facility or microorganisms actively grow in a place where water is recycled, it causes fouling, which not only lowers the heat transfer efficiency but also corrodes the metal. Or erosion of wood.

Bacteria are proliferation of unicellular prokaryotes, which can proliferate while decomposing various kinds of organic substances, and some of them secrete polysaccharides to the outside to form biofilms, causing microbiologically induced corrosion. Fungi are eukaryotes, which can grow by decomposing various kinds of organic substances similar to bacteria, and the types of cellulase that secrete cellulase break down the fiber of wood parts such as cooling towers to discolor and decay wood parts. Cause.

Algae are also eukaryotes, which can multiply by photosynthesis under light, air, and small amounts of minerals. Carbohydrates produced by algae are used as nutrients for other microorganisms, such as bacteria and fungi, to accelerate fouling. Let's do it. Particularly in the sun exposed areas such as cooling water facilities and swimming pools, the fouling phenomenon due to the growth of algae is intensified, causing clogging of water pipes, reducing heat transfer efficiency, and reducing oxygen. Not only oxidizes the metal surface, but also causes local corrosion to promote corrosion at the hole of the metal when killed.

In order to kill such microorganisms, mold, algae, or the like to prevent surface adhesion to metals, various fungicides have been developed, and such fungicides are generally classified into oxidizing fungicides and non-oxidizing fungicides. Halogen compounds such as chlorine and bromine are mainly used as oxidizing fungicides, and they are widely used in terms of economy because of their high oxidizing power and low cost, but they cause wood erosion and metal corrosion of cooling towers, and they are easily released into the atmosphere, which is effective in disinfecting. In addition to the deterioration, in particular, non-specific reactions in the biofilm-forming state before reacting with the causative microorganisms (Polysaccharides) secreted before they react, there is a disadvantage that the effective sterilization effect is lowered.

Non-oxidizing fungicides that overcome such disadvantages are known as 3-isothiazolone, quaternary ammonium compound, formaldehyde releasing compound, glutaraldehyde and the like, which are mainly used alone. 3-isothiazolones described in U.S. Patent Nos. 3,761,488, 4,105,431, 4,279,762 and the like have a high bactericidal effect and a broad antimicrobial spectrum, but have a disadvantage of low instantaneous effect and low instantaneous bactericidal effect. In addition, Korean Patent Application No. 89-20381 discloses 5-chloro-2-methyl-4-isothiazolone-3-one and 2-methyl-4-isothiazolone-3 as an antiseptic composition useful for preventing corruption of circulating water. A sterilizer is disclosed which contains -one at about 3: 1 and further contains didecyldimethylammonium chloride. US Pat. No. 4,379,137 combines quaternary ammonium compounds of polymers and 3-isothiazolones to improve sterilization. Although the method is disclosed, such a mixture emits halogen compounds such as fluorine and chlorine, which are corrosive substances, and thus has a disadvantage in that it is difficult to apply where corrosive metals such as carbon steel, cast iron, stainless steel, and copper are used.

In addition, Korean Patent Application No. 97-80170 can be applied to a process using corrosive metal because it does not emit a halogen compound, and it is an excellent disinfectant with excellent instantaneous sterilization, persistence, and corrosion resistance against microorganisms. A synergistic, water-soluble bactericide composition comprising quaternary ammonium phosphate described in US Pat. No. 46517 and 3-isothiazolone having high bactericidal properties against microorganisms is disclosed. However, when the quaternary ammonium is added to give 3-isothiazolone as a fast-acting agent, problems such as foaming are caused, which makes it difficult to apply to various industrial fields.

In addition, polyhexamethyleneguanidine phosphate has a short-acting effect, it is used for more effective and extensive control of microorganisms in various industries, such as water treatment and disinfectants, and less foaming, but has the disadvantage that the antimicrobial spectrum itself is not wide.

Therefore, the present invention can be used in a process in which corrosive metals such as carbon steel, cast iron, stainless steel, copper, etc. are used, as well as to provide a disinfectant composition having high instantaneous sterilizing power, broad antibacterial spectrum, and excellent antiseptic effect. do.

It is also an object of the present invention to provide a fungicide composition which is low in foaming property and can be applied to various industrial processes as well as high sterilizing power even when a small amount is used.

In order to achieve the above object, the present invention provides a disinfectant composition comprising 3-isothiazolone of formula (1) and polyhexamethyleneguanidine phosphate of formula (2).

[Formula 1]

[Formula 2]

In Formula 1, R is hydrogen or chlorine, m in Formula 2 is an integer of 4 to 7, n is an integer of 1 to 14. The present invention also provides a sterilization method in which the fungicide composition is injected into a region contaminated by bacteria, fungi and algae to kill the bacteria, fungi or algae, or to inhibit growth.

Hereinafter, the present invention will be described in detail.

The present invention provides an antiseptic and / or fungicide composition comprising 3-isothiazolone of Chemical Formula 1 and polyhexamethyleneguanidine phosphate of Chemical Formula 2. Wherein the 3-isothiazolone is 2-methyl-4-isothiazolone-3-one in which the R group is hydrogen or 5-chloro-2-methyl-4-isothiazolone in which the R group is chlorine It is preferably 3-one, and more preferably 2-methyl-4-isothiazolone-3-one and 5-chloro-2-methyl-4-isothiazolone-3-one are 1:20 to 20: It is good that it is a mixture mixed in the weight ratio of 1. If the ratio of the 3-isothiazolone compound is 1:20 to 20: 1, the bactericidal effect is lowered.

The mixing ratio of the 3-isothiazolone and polyhexamethyleneguanidine phosphate is preferably 1: 1 to 1:65 by weight, more preferably 1: 1 to 1: 4. If the mixing ratio of the 3-isothiazolone and polyhexamethyleneguanidine phosphate is out of the above range, the synergistic effect of the mixing of the two fungicides is not reduced or shown.

When the 3-isothiazolone and polyhexamethyleneguanidine phosphate mixture of the present invention is used as a disinfectant composition, 3-isothiazolone compensates for the disadvantage that the polyhexamethyleneguanidine phosphate has a poor bactericidal effect against mold and some bacteria, and 3 Not only does polyhexamethyleneguanidine phosphate compensate for the short-term disinfection and short-acting shortcomings of isothiazolones, but the sterilization of mixed fungicides has a synergistic effect that is greater than the sum of the sterilization actions of each compound. In other words, by using two kinds of compounds having different sterilization mechanisms, the composition of the present invention can suppress microorganisms more effectively and extensively, and can obtain the expected effect of lowering the frequency of resistant strains when used alone. .

The disinfectant composition of the present invention is preferably dissolved in water and used in the form of an aqueous solution. The disinfectant composition of the present invention is not limited to the amount used as long as it exhibits the desired sterilizing effect. desirable. The disinfectant composition of the present invention can be used for effective and extensive control of microorganisms in various industrial fields such as pulp and paper mills, cooling towers and disinfectants, and especially additives for cooling water, disinfectants, paints, latex preservatives and cosmetics in industrial processes. , Additives in emulsion products such as shampoos, anti-rust agents for textile fabrics, paper slime control agents, preservatives for leather products, and preservatives for metal processing oils.

Hereinafter, comparative examples and non-limiting, preferred examples for the understanding of the present invention will be described.

Example 1-6

A mixture of bacteria, eight kinds (Enterobacter aerogens ATCC 13048, Escherichia coli ATCC 11229, Micrococcus luteus ATCC 9341, Pseudomonas aeruginosa ATCC 15442, Klebsiella pneumoniae ATCC 1560, Staphylococcus epidermis ATCC 155, Staphylococcus aureus ATCC 6538, 8 species of Bacillus subtilis ATCC 6984) The bactericidal effect of 3-isothiazolone and polyhexamethyleneguanidine phosphate was tested according to the two-fold dilution method using Tryptic Soy Broth (Difco). After incubating the culture medium containing the fungicide and microorganism for 3 days at 30 ° C., the lowest concentration of turbidity that inhibited growth was visually observed and the minimum growth inhibition concentration (MIC) of each fungicide and fungicide mixture was determined. .

The synergism of the fungicide is Kull, F.C. According to the method published in et al. (Appl. Microbiol. 9: 538 to 544 (1961)), it is determined by the following formula that synergy occurs when the sum of QA / Qa and QB / Qb is less than 1. The results are shown in Table 1.

Ascent index (SI) = (QA / Qa) + (QB / Qb)

Wherein Qa and Qb are the MIC values (ppm) of compounds A and B alone, respectively, and QA and QB are the MIC values (ppm) of compounds A and B in the mixture, respectively.

Synergistic test results of fungicide mixtures (for bacteria) Qa Qb QA QB QA / Qa QB / Qb SI Example 1 18.8 312.5 9.4 9.8 0.5 0.03 0.53 Example 2 18.8 312.5 9.4 19.5 0.5 0.06 0.56 Example 3 18.8 312.5 9.4 39.1 0.5 0.13 0.63 Example 4 18.8 312.5 9.4 78.1 0.5 0.25 0.75 Example 5 18.8 312.5 9.4 156.3 0.5 0.50 1.0 Example 6 18.8 312.5 2.4 156.3 0.13 0.50 0.63

Qa: MIC value (ppm) of mixed strain of 3-isothiazolone alone

Qb: MIC value (ppm) of mixed strain of polyhexamethyleneguanidine phosphate alone

QA: MIC of 3-isothiazolone in the mixture (ppm)

QB: MIC value of polyhexamethyleneguanidine phosphate in the mixture (ppm)

As shown in Table 1, the same microorganism killing effect (Example 1, SI = 0.53) can be obtained even when only 3-isothiazolone is used and the amount of polyhexamethyleneguanidine phosphate is reduced to 9.8 ppm. In addition, it can be seen that even when only 1/2 of polyhexamethyleneguanidine phosphate and 2.4 ppm of 3-isothiazolone are used, the killing effect of the same microorganism (Example 6, SI = 0.63) can be obtained. Therefore, when the two compounds are mixed, the growth of bacteria can be more effectively inhibited than when the two substances are used alone, and the synergistic ratio of 3-isothiazolone and polyhexamethyleneguanidine phosphate is about 1: 1. It is understood that the most preferable (SI: 0.53 to 0.63) in the range of 1 to 1: 4.

[Test Example 1 and Comparative Example 1]

Sterilization of 3-isothiazolone and polyhexamethyleneguanidine phosphate components in a ratio of 1: 4 (1 wt% of 3-isothiazolone and 15 wt% of 25 wt% polyhexamethyleneguanidine phosphate) for 7 individual strains MIC values of the composition and 1.5 wt% 3-isothiazolone alone bactericide were measured. The MIC test was performed by diluting the fungicide using a 96 multi-well plate according to the 2-fold serial dilution method, inoculating the microorganism at a concentration of 104 CFU / mL, and incubating for 48 hours at 30 ° C. The MIC value was measured by the method of visual inspection as a reference, and the result is shown in Table 2.

In order to measure the MIC value, the turbidity was observed using Tryptic Soy Broth, Difco Co. as a medium, and the strain used was Enterobacter aerogens ATCC 13048, Staphylococcus aureus ATCC 6538, Staphylococcus epidermis ATCC 155, Bacillus subtilis ATCC 6984, Saccharomyces cerevisiae ATCC 9763, Rhizopus oryzae ATCC 10404, Aspergillus niger ATCC 9642 were used.

MIC test results for microorganisms of fungicide mixture and 1.5 wt% 3-isothiazolone alone fungicide (unit: ppm). Use strain Comparative Example (1.5% isothiazolone) Test Example (Fungicide Mixture) Enterobacter aerogens ATCC 13048 390 195 Staphylococcus aureus ATCC 6538 195 195 Staphylococcus epidermis ATCC 155, 390 97 Bacillus subtilis ATCC 6984 390 195 Saccharomyces cerevisiae ATCC 9763 390 390 Rhizopus oryzae ATCC 10404 390 195 Aspergillus niger ATCC 9642 195 195

As can be seen from Table 2, the fungicide mixture of 3-isothiazolone and 25 wt% polyhexamethyleneguanidine phosphate was mixed using an elevated index, rather than 1.5 wt% 3-isothiazolone alone. It is much more effective in controlling.

[Test Example 2 and Comparative Example 2]

The fungicide mixture used in Test Example 1 and the 1.5% 3-isothiazolone solution used in Comparative Example 1 had a microbial concentration of about 104 CFU / to determine the killing time, efficacy and persistence of the solution. After disinfecting the fungicide mixture and 1.5% 3-isothiazolone in 50ml, 100ppm and 200ppm of the cooling water of the polymerization cooling tower of ml, respectively, immediately after the addition (0 min), 3 hours, 24 hours, 48 hours, 72 hours, 96 hours The bacteria were collected at intervals and the number of bacteria was measured. At this time, the solution to which the fungicide was not added was set as a blank. The results of measuring the strain reduction rate of the fungicide mixture in which 3-isothiazolone and polyhexamethyleneguanidine phosphate were mixed using a synergistic index and 1.5 wt% 3-isothiazolone alone fungicide with time are shown in Tables 3 and 4.

Result of microbial reduction rate by concentration and time of fungicide mixture (unit: CFU / mL) 0 hours 3 hours 24 hours 48 hours 72 hours 96 hours Blank 13000 > 13000 > 13000 > 13000 > 13000 > 13000 Fungicide mixtures 50 ppm 13000 210 140 90 40 50 100 ppm 13000 80 170 90 50 30 200 ppm 13000 50 90 50 40 50

Result of measurement of microbial reduction rate with concentration and time of 1.5% by weight 3-isothiazolone (unit: CFU / mL) 0 hours 3 hours 24 hours 48 hours 72 hours 96 hours Blank 13000 > 13000 > 13000 > 13000 > 13000 > 13000 1.5% Isothiazolone 50 ppm 13000 12000 450 > 10000 > 10000 > 10000 100 ppm 13000 11400 370 6250 > 10000 > 10000 200 ppm 13000 5300 200 2100 > 10000 > 10000

As can be seen from Tables 3 and 4, in the case of 1.5% by weight of 3-isothiazolone alone, bactericidal power was exhibited after 24 hours, but the fast-acting effect was decreased, and after 48 hours in the presence of organic matter, secondary growth of the microorganisms occurred. In contrast, the disinfectant mixture of 3-isothiazolone and polyhexamethyleneguanidine phosphate using a synergistic index is not only fast-acting and lasting, but also has a superior bactericidal effect against microorganisms. . Therefore, when 3-isothiazolone and polyhexamethyleneguanidine phosphate are mixed, the disadvantages of the fastness of 3-isothiazolone and the problem of antimicrobial spectrum of polyhexamethyleneguanidine phosphate complement each other. It can be seen that there is a correlation.

As described above, the disinfectant composition of the present invention has a wide range of antimicrobial spectra, with fastness and persistence, and thus is effectively used for a wide range of microorganisms in various industrial fields such as water treatment and disinfectant. In addition, the fungicide composition of the present invention is more effective than the single compound in controlling the microorganisms and has a greater instantaneous sterilizing power, so that the microorganisms can effectively control the industrial water and microorganisms in the living environment, and use a mixed fungicide with different functional mechanisms. By doing so, there is an effect of lowering the frequency of appearance of resistant strains when used alone.

Claims (4)

A sterilant composition comprising 3-isothiazolone of formula 1 and polyhexamethyleneguanidine phosphate of formula 2 in a weight ratio of 1: 1 to 1:65. [Formula 1] [Formula 2] In Formula 1, R is hydrogen or chlorine, m in Formula 2 is an integer of 4 to 7, n is an integer of 1 to 14. The method of claim 1, wherein the 3-isothiazolone is a mixture of 3-isothiazolone, in which R is hydrogen, and 3-isothiazolone, in which R is chlorine, in a weight ratio of 1:20 to 20: 1. -Fungicide composition wherein the mixing ratio of isothiazolone and polyhexamethyleneguanidine phosphate is 1: 1 to 1: 4. The method of claim 1, wherein the disinfectant composition is an industrial process cooling water, disinfectant, paint, latex preservatives, cosmetic additives, additives of emulsion products, textile weaving anti-rust agent, paper sludge control agent, leather preservatives and metals A fungicide composition, characterized in that used in combination with a compound selected from the group consisting of preservatives for processing oil. A sterilization method in which the bactericidal composition of claim 1 is added to a region contaminated by bacteria, mold and / or algae to kill the bacteria, mold and / or algae, or to inhibit growth.